TlPbPS₄

The quaternary thallium thio­phosphate TlPbPS₄ (thallium lead phospho­rus tetra­sulfide) was obtained by reacting elemental Pb with a melt, formed in situ, of Tl₂S, P₂S₅ and S. The crystal structure is composed of parallel zigzag layers, which consist of condensed S₆ distorted trigonal prisms alternately centred by Tl and Pb atoms. The layers are stacked perpendicular to the crystallographic a axis and are joined by [PS₄] tetra­hedra. TlPbPS₄ is isostructural with TlEuPS₄ and TlSnPS₄.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](S-P) = 0.005 Å
• R factor = 0.046
• wR factor = 0.125
• Data-to-parameter ratio = 22.5

checkCIF/PLATON results

No syntax errors found



Alert level C
CRYSC01_ALERT_1_C No recognised colour has been given for crystal colour.
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.114
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.11
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT126_ALERT_1_C Error in or Uninterpretable Hall Symbol  .......    P N M A
PLAT127_ALERT_1_C Implicit Hall Symbol  Inconsistent with Explicit    P n m a

Alert level G
ABSTM02_ALERT_3_G  The ratio of expected to reported Tmax/Tmin(RR') is < 0.75
            Tmin and Tmax reported:      0.004     0.046
            Tmin(prime) and Tmax expected:      0.015     0.090
            RR(prime) =      0.567
            Please check that your absorption correction is appropriate.
CHEMS02_ALERT_1_G  Please check that you have entered the correct
            _publ_requested_category classification of your compound;
            FI or CI or EI for inorganic; FM or CM or EM for metal-organic;
            FO or CO or EO for organic.
            From the CIF: _publ_requested_category   EO
            From the CIF: _chemical_formula_sum:P1 Pb1 S4 Tl1
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: IPDS Program Package (Stoe & Cie, 1998); cell refinement: IPDS Program Package (Stoe & Cie, 1998); data reduction: IPDS Program Package; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia,1997) and BS (Ozawa & Kang, 2004); software used to prepare material for publication: SHELXL97.

Thallium lead tetrathiophosphate

Crystal data

TlPbPS4	F(000) = 968
Mr = 570.77	Dx = 5.405 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P n m a	Cell parameters from 921 reflections
a = 12.0976 (9) Å	θ = 2.9–28.0°
b = 6.5816 (5) Å	µ = 48.21 mm^−1
c = 8.8093 (6) Å	T = 293 K
V = 701.41 (9) Å^3	Platelets, dark
Z = 4	0.08 × 0.06 × 0.05 mm

Data collection

Stoe IPDS diffractometer	921 independent reflections
Radiation source: fine-focus sealed tube	743 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.114
ω scans	θmax = 28.0°, θmin = 2.9°
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998)	h = −15→15
Tmin = 0.005, Tmax = 0.046	k = −8→8
4828 measured reflections	l = −11→11

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	w = 1/[σ^2(Fo^2) + (0.0775P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.125	(Δ/σ)max < 0.001
S = 1.00	Δρmax = 2.57 e Å^−3
921 reflections	Δρmin = −3.30 e Å^−3
41 parameters	Extinction correction: SHELXL97
0 restraints	Extinction coefficient: 0.0021 (3)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Tl1	0.39716 (8)	0.7500	0.62788 (8)	0.0396 (3)
Pb1	0.63273 (6)	0.2500	0.89495 (8)	0.0307 (3)
P1	0.3444 (3)	0.2500	0.8748 (4)	0.0160 (7)
S1	0.4489 (4)	0.2500	0.6937 (4)	0.0268 (9)
S2	0.4309 (4)	0.2500	1.0748 (4)	0.0270 (9)
S3	0.2446 (2)	0.0010 (5)	0.8644 (4)	0.0266 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Tl1	0.0477 (5)	0.0418 (5)	0.0294 (4)	0.000	−0.0038 (3)	0.000
Pb1	0.0239 (4)	0.0446 (5)	0.0236 (4)	0.000	0.0001 (2)	0.000
P1	0.0177 (16)	0.0130 (18)	0.0174 (17)	0.000	−0.0009 (14)	0.000
S1	0.033 (2)	0.033 (2)	0.0140 (16)	0.000	0.0006 (17)	0.000
S2	0.0243 (19)	0.041 (3)	0.0155 (17)	0.000	−0.0013 (16)	0.000
S3	0.0278 (14)	0.0182 (15)	0.0338 (16)	−0.0035 (11)	−0.0050 (12)	0.0010 (11)

Geometric parameters (Å, º)

Pb1—S1	2.844 (4)	P1—S1	2.035 (6)
Pb1—S2	2.911 (4)	P1—S3	2.038 (4)
Pb1—S3^i	3.070 (3)	P1—S3^v	2.038 (4)
Pb1—S3^ii	3.070 (3)	P1—S2	2.050 (5)
Pb1—S3^iii	3.120 (3)	S3—Pb1^ii	3.070 (3)
Pb1—S3^iv	3.120 (3)	S3—Pb1^vi	3.120 (3)
S1—Pb1—S2	71.53 (12)	S3^ii—Pb1—S3^iv	125.35 (2)
S1—Pb1—S3^i	143.95 (6)	S3^iii—Pb1—S3^iv	63.37 (11)
S2—Pb1—S3^i	91.71 (9)	S1—P1—S3	109.45 (16)
S1—Pb1—S3^ii	143.95 (6)	S1—P1—S3^v	109.45 (16)
S2—Pb1—S3^ii	91.71 (9)	S3—P1—S3^v	107.1 (3)
S3^i—Pb1—S3^ii	65.09 (11)	S1—P1—S2	110.9 (3)
S1—Pb1—S3^iii	83.26 (9)	S3—P1—S2	109.94 (15)
S2—Pb1—S3^iii	139.66 (7)	S3^v—P1—S2	109.94 (15)
S3^i—Pb1—S3^iii	125.35 (2)	P1—S1—Pb1	89.85 (17)
S3^ii—Pb1—S3^iii	90.764 (13)	P1—S2—Pb1	87.73 (17)
S1—Pb1—S3^iv	83.26 (9)	P1—S3—Pb1^ii	96.62 (14)
S2—Pb1—S3^iv	139.66 (7)	P1—S3—Pb1^vi	82.37 (13)
S3^i—Pb1—S3^iv	90.764 (13)	Pb1^ii—S3—Pb1^vi	176.20 (12)

Symmetry codes: (i) −x+1, y+1/2, −z+2; (ii) −x+1, −y, −z+2; (iii) x+1/2, y, −z+3/2; (iv) x+1/2, −y+1/2, −z+3/2; (v) x, −y+1/2, z; (vi) x−1/2, y, −z+3/2.